阅读说明：本技术 一种基于硅铝基空心微珠增强尼龙板材及其制备工艺 (Reinforced nylon plate based on silicon-aluminum-based hollow microspheres and preparation process thereof ) 是由 吴光辉 于 2020-07-30 设计创作，主要内容包括：本发明公开了一种基于硅铝基空心微珠增强尼龙板材及其制备工艺,该尼龙板材由如下重量份原料制成：己内酰胺100-120份、硅铝基空心微珠3-5份、热稳定填料3-5份、抗静电剂1-3份；并在制备过程中制备了硅铝基空心微珠和热稳定填料,该硅铝基空心微珠将硅离子和铝离子接枝到玻璃微珠上,大大增强尼龙板的耐摩擦性和抗冲击性,进而提升了尼龙板的使用寿命,该热稳定填料能够捕捉尼龙扳中的大分子自由基,进而与大分子自由基进行反应,使得自由基终止,进而防止自由基继续反应,从而达到耐热效果,保证了在尼龙板长时间使用的过程中,热稳定分子不会与本体分离,使得尼龙板的使用寿命增长,且不易析出,有效了避免对环境造成污染。(The invention discloses a silicon-aluminum-based hollow microsphere-based reinforced nylon plate and a preparation process thereof, wherein the nylon plate is prepared from the following raw materials in parts by weight: 100-120 parts of caprolactam, 3-5 parts of silicon-aluminum-based hollow microspheres, 3-5 parts of heat-stable filler and 1-3 parts of antistatic agent; and silicon-aluminum-based hollow microspheres and thermal stable filler are prepared in the preparation process, the silicon-aluminum-based hollow microspheres graft silicon ions and aluminum ions onto the glass microspheres, the friction resistance and the impact resistance of the nylon plate are greatly enhanced, the service life of the nylon plate is further prolonged, the thermal stable filler can capture macromolecular free radicals in the nylon plate, and then the macromolecular free radicals react with the macromolecular free radicals, so that the free radicals are terminated, and further the free radicals are prevented from continuing to react, thereby the heat-resistant effect is achieved, the thermal stable molecules can not be separated from the body in the long-time use process of the nylon plate, the service life of the nylon plate is prolonged, the separation is not easy, and the environmental pollution is effectively avoided.)

1. A nylon plate based on silicon-aluminum-based hollow micro-beads is characterized in that: the feed is prepared from the following raw materials in parts by weight: 100-120 parts of caprolactam, 3-5 parts of silicon-aluminum-based hollow microspheres, 3-5 parts of heat-stable filler and 1-3 parts of antistatic agent;

the nylon plate is prepared by the following steps:

step S1: adding the silicon-aluminum-based hollow microspheres, the heat-stable filler, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring at the rotating speed of 300-500r/min until the silicon-aluminum-based hollow microspheres and the heat-stable filler are uniformly dispersed to prepare a dispersion liquid;

step S2: heating caprolactam at 75-80 ℃ until the caprolactam is completely melted, adding the dispersion liquid and the antistatic agent prepared in the step S1, stirring for 15-20min at the rotation speed of 100-150r/min, carrying out ultrasonic treatment for 5-10min at the frequency of 5-8MHz, heating to the temperature of 130-150 ℃, drying, pressing, and cooling to room temperature to obtain the nylon plate.

2. The silicon-aluminum-based hollow microsphere reinforced nylon plate material as claimed in claim 1, which is characterized in that: the antistatic agent is one of dodecyl dimethyl quaternary ethyl inner salt and dodecyl dimethyl aminoethylenolactone.

3. The silicon-aluminum-based hollow microsphere reinforced nylon plate material as claimed in claim 1, which is characterized in that: the silicon-aluminum-based hollow microsphere is prepared by the following steps:

step A1: adding aluminum chloride and deionized water into a reaction kettle, and carrying out ultrasonic treatment for 15-20min under the condition of frequency of 30-50kHz to prepare an aluminum chloride solution;

step A2: adding ethyl orthosilicate, ethanol and hydrochloric acid solution into a reaction kettle, and stirring for 20-30min at the rotation speed of 300-500r/min and at the temperature of 25-30 ℃ to obtain silica sol;

step A3: adding the aluminum chloride solution prepared in the step A1 into a reaction kettle, stirring and dropwise adding the silica gel solution prepared in the step A2 at the rotation speed of 200-300r/min and the temperature of 50-60 ℃, wherein the dropwise adding speed is 1-3mL/min, and after the dropwise adding is finished, continuously stirring for 3-5h to prepare a silicon-aluminum-based mixed solution;

step A4: adding glass powder, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring at the rotation speed of 500-plus-800 r/min to obtain a mixture, ball-milling the mixture until the particle size is 100-plus-150 meshes, adding calcium carbonate and magnesium carbonate into the mixture, adding the silicon-aluminum-based mixed solution prepared in the step A3, continuously stirring for 2-4h at the rotation speed of 600-plus-800 r/min and at the temperature of 25-30 ℃, carrying out centrifugal atomization at the rotation speed of 5000-plus-6000 r/min to obtain atomized microbeads, drying the atomized microbeads, and calcining for 4-5h at the temperature of 600-plus-800 ℃ to obtain the silicon-aluminum-based hollow microbeads.

4. The silicon-aluminum-based hollow microsphere reinforced nylon plate material is characterized in that: the using amount ratio of the aluminum chloride and the deionized water in the step A1 is 1-3g:20mL, the using amount volume ratio of the ethyl orthosilicate, the ethanol and the hydrochloric acid solution in the step A2 is 14:2:1.5-2, the mass fraction of the hydrochloric acid solution is 16-18%, the using amount volume ratio of the aluminum chloride solution and the silica sol solution in the step A3 is 1-1.5:2, the using amount ratio of the glass powder and the deionized water in the step A4 is 1g:5mL, the using amount of the sodium dodecyl benzene sulfonate is 2-5% of the glass powder, and the using amount ratio of the mixture, the calcium carbonate, the magnesium carbonate and the silicon-aluminum base mixed solution is 5g: 0.1g, 3-5 mL.

5. The silicon-aluminum-based hollow microsphere reinforced nylon plate material as claimed in claim 1, which is characterized in that: the heat-stable filler is prepared by the following steps:

step B1: adding carbon nano tubes into first mixed acid for soaking, performing ultrasonic treatment for 1-3h under the conditions that the frequency is 30-50kHz and the temperature is 50-55 ℃, adding deionized water for stirring until the mixture is uniformly mixed, standing for 3-5h, removing supernatant, washing precipitates with distilled water until the pH value of the surfaces of the precipitates is 7, and preparing acidified carbon nano tubes;

step B2: adding thionyl chloride, N-dimethylformamide and the acidified carbon nano tube prepared in the step B1 into a reaction kettle, stirring at the rotation speed of 100-80 ℃ for 20-25h, filtering to remove reaction liquid, washing a filter cake with tetrahydrofuran until the washing liquid is clear, drying the filter cake, adding the filter cake and ethylenediamine into the reaction kettle, stirring at the rotation speed of 60-80r/min and the temperature of 100-80 ℃ for 30-40h to obtain a reactant, washing the reactant with ethanol until the washing liquid is clear, and drying the reactant to prepare the amino carbon nano tube;

step B3: mixing maleic anhydride and N, N-dimethylacetamide until the maleic anhydride is completely dissolved to obtain a maleic anhydride solution, adding the maleic anhydride solution into a reaction kettle, dropwise adding a second mixed acid at the rotation speed of 60-80r/min and the temperature of 50-55 ℃, wherein the dropwise adding time is 1-1.2h, continuously stirring for 15-20min after the dropwise adding is finished to obtain an intermediate 1, adding the intermediate 1 and a hydrochloric acid solution into the reaction kettle, stirring for 15-20min at the rotation speed of 60-80r/min and the temperature of 95-98 ℃, adding sodium hydroxide until the pH value of a reaction solution is 9-10, and filtering to remove filtrate to obtain an intermediate 2;

step B4: adding chlorobenzene and the intermediate 2 prepared in the step B3 into a reaction kettle, stirring until the intermediate 2 is completely dissolved under the conditions that the rotation speed is 100-150r/min and the temperature is 35-45 ℃, introducing phosgene, heating to the temperature of 130-135 ℃ for reaction for 1-1.5h, and introducing nitrogen to remove the phosgene to prepare an intermediate 3;

step B5: adding dibutyltin dichloride and toluene into a reaction kettle, stirring at the rotation speed of 100-200r/min and at the temperature of 40-50 ℃ until dibutyltin dichloride is completely dissolved, dropwise adding a sodium hydroxide solution, reacting for 2-3h to obtain an intermediate 4, adding the intermediate 4, tetrahydrofuran and the intermediate 3 prepared in the step B4 into the reaction kettle, reacting for 2-2.5h at the temperature of 50-60 ℃, and distilling at the temperature of 70-80 ℃ to remove tetrahydrofuran to obtain an intermediate 5;

step B6: and B5, adding the intermediate 5 and tetrahydrofuran into a reaction kettle, stirring until the intermediate 5 is completely dissolved, adding N, N-diisopropylethylamine and the amino carbon nanotube prepared in the step B2, stirring for 20-30min under the conditions that the rotation speed is 150-200r/min and the temperature is 20-30 ℃, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 20-50kHz, filtering to remove filtrate, and drying a filter cake to obtain the heat-stable filler.

6. The silicon-aluminum-based hollow microsphere reinforced nylon plate material is characterized in that: the first mixed acid described in the step B1 is prepared by mixing concentrated nitric acid and concentrated sulfuric acid with a volume ratio of 1:3, the mass fraction of the concentrated nitric acid is 68-70%, the mass fraction of the concentrated sulfuric acid is 70-75%, the dosage ratio of the thionyl chloride, the N, N-dimethylformamide and the acidified carbon nanotube described in the step B2 is 60mL:3mL:1-3g, the dosage ratio of the filter cake and the ethylenediamine is 1-3g:120mL, the dosage ratio of the maleic anhydride and the second mixed acid described in the step B3 is 1g:2-3mL, the second mixed acid is prepared by mixing concentrated nitric acid and concentrated sulfuric acid with a volume ratio of 9:10, the mass fraction of the concentrated nitric acid is 70-75%, the mass fraction of the concentrated sulfuric acid is 75-80%, the dosage ratio of the intermediate 1-1.5g:4mL and the hydrochloric acid solution is 38-40%, the dosage ratio of the intermediate 2 and phosgene described in the step B4 is 1:3, the mass ratio of the dibutyltin dichloride and the sodium hydroxide solution in the step B5 is 1:2, the mass fraction of the sodium hydroxide solution is 30-35%, the mass ratio of the intermediate 4 to the intermediate 3 is 1:1, the mass ratio of the intermediate 5 to the amino carbon nanotube in the step B6 is 5-6:3, and the amount of N, N-diisopropylethylamine is 5-8% of the total weight of the intermediate 5 and the amino carbon nanotube.

7. The preparation process of the silicon-aluminum-based hollow microsphere-based reinforced nylon plate material according to claim 1, characterized by comprising the following steps: the method comprises the following steps:

step S1: adding the silicon-aluminum-based hollow microspheres, the heat-stable filler, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring at the rotating speed of 300-500r/min until the silicon-aluminum-based hollow microspheres and the heat-stable filler are uniformly dispersed to prepare a dispersion liquid;

step S2: heating caprolactam at 75-80 ℃ until the caprolactam is completely melted, adding the dispersion liquid and the antistatic agent prepared in the step S1, stirring for 15-20min at the rotation speed of 100-150r/min, carrying out ultrasonic treatment for 5-10min at the frequency of 5-8MHz, heating to the temperature of 130-150 ℃, drying, pressing, and cooling to room temperature to obtain the nylon plate.

Technical Field

The invention belongs to the technical field of plate preparation, and particularly relates to a silicon-aluminum-based hollow microsphere-based reinforced nylon plate and a preparation process thereof.

Background

The Polyamide is generally called Nylon (Nylon), and is named after the name Polyamide (PA for short) because the molecular main chain contains repeated amide groups [ NHCO ], and is a basic resin with the largest yield, the largest variety, the widest application and excellent comprehensive performance in five general engineering plastics.

The existing nylon plate can be rubbed and impacted in the using process, the part rubbed or impacted is deeply damaged due to poor self wear resistance and impact resistance, the service life of the nylon plate is shortened, the nylon plate can be oxidized due to overhigh temperature in the using process, the performance of the nylon plate is reduced, and the service life of the nylon plate is greatly shortened.

Disclosure of Invention

The invention aims to provide a silicon-aluminum-based hollow microsphere-based reinforced nylon plate and a preparation process thereof.

The technical problems to be solved by the invention are as follows:

the existing nylon plate can be rubbed and impacted in the using process, the part rubbed or impacted is deeply damaged due to poor self wear resistance and impact resistance, the service life of the nylon plate is shortened, the nylon plate can be oxidized due to overhigh temperature in the using process, the performance of the nylon plate is reduced, and the service life of the nylon plate is greatly shortened.

The purpose of the invention can be realized by the following technical scheme:

a reinforced nylon plate based on silicon-aluminum-based hollow microspheres is prepared from the following raw materials in parts by weight: 100-120 parts of caprolactam, 3-5 parts of silicon-aluminum-based hollow microspheres, 3-5 parts of heat-stable filler and 1-3 parts of antistatic agent;

the nylon plate is prepared by the following steps:

step S1: adding the silicon-aluminum-based hollow microspheres, the heat-stable filler, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring at the rotating speed of 300-500r/min until the silicon-aluminum-based hollow microspheres and the heat-stable filler are uniformly dispersed to prepare a dispersion liquid;

step S2: heating caprolactam at 75-80 ℃ until the caprolactam is completely melted, adding the dispersion liquid and the antistatic agent prepared in the step S1, stirring for 15-20min at the rotation speed of 100-150r/min, carrying out ultrasonic treatment for 5-10min at the frequency of 5-8MHz, heating to the temperature of 130-150 ℃, drying, pressing, and cooling to room temperature to obtain the nylon plate.

Further, the antistatic agent is one of dodecyl dimethyl quaternary ethyl inner salt and dodecyl dimethyl aminoethylenolactone.

Further, the silicon-aluminum-based hollow microsphere is prepared by the following steps:

step A1: adding aluminum chloride and deionized water into a reaction kettle, and carrying out ultrasonic treatment for 15-20min under the condition of frequency of 30-50kHz to prepare an aluminum chloride solution;

step A2: adding ethyl orthosilicate, ethanol and hydrochloric acid solution into a reaction kettle, and stirring for 20-30min at the rotation speed of 300-500r/min and at the temperature of 25-30 ℃ to obtain silica sol;

step A3: adding the aluminum chloride solution prepared in the step A1 into a reaction kettle, stirring and dropwise adding the silica gel solution prepared in the step A2 at the rotation speed of 200-300r/min and the temperature of 50-60 ℃, wherein the dropwise adding speed is 1-3mL/min, and after the dropwise adding is finished, continuously stirring for 3-5h to prepare a silicon-aluminum-based mixed solution;

step A4: adding glass powder, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, stirring at the rotation speed of 500-plus-800 r/min to obtain a mixture, ball-milling the mixture until the particle size is 100-plus-150 meshes, adding calcium carbonate and magnesium carbonate into the mixture, adding the silicon-aluminum-based mixed solution prepared in the step A3, continuously stirring for 2-4h at the rotation speed of 600-plus-800 r/min and at the temperature of 25-30 ℃, carrying out centrifugal atomization at the rotation speed of 5000-plus-6000 r/min to obtain atomized microbeads, drying the atomized microbeads, and calcining for 4-5h at the temperature of 600-plus-800 ℃ to obtain the silicon-aluminum-based hollow microbeads.

Further, the using amount ratio of the aluminum chloride and the deionized water in the step A1 is 1-3g:20mL, the using amount volume ratio of the ethyl orthosilicate, the ethanol and the hydrochloric acid solution in the step A2 is 14:2:1.5-2, the mass fraction of the hydrochloric acid solution is 16-18%, the using amount volume ratio of the aluminum chloride solution and the silica sol solution in the step A3 is 1-1.5:2, the using amount ratio of the glass powder and the deionized water in the step A4 is 1g:5mL, the using amount of the sodium dodecyl benzene sulfonate is 2-5% of the glass powder, and the using amount ratio of the mixture, the calcium carbonate, the magnesium carbonate and the silicon-aluminum base mixed solution is 5g: 0.1g, 3-5 mL.

Further, the heat-stable filler is prepared by the following steps:

step B1: adding carbon nano tubes into first mixed acid for soaking, performing ultrasonic treatment for 1-3h under the conditions that the frequency is 30-50kHz and the temperature is 50-55 ℃, adding deionized water for stirring until the mixture is uniformly mixed, standing for 3-5h, removing supernatant, washing precipitates with distilled water until the pH value of the surfaces of the precipitates is 7, and preparing acidified carbon nano tubes;

step B2: adding thionyl chloride, N-dimethylformamide and the acidified carbon nano tube prepared in the step B1 into a reaction kettle, stirring at the rotation speed of 100-80 ℃ for 20-25h, filtering to remove reaction liquid, washing a filter cake with tetrahydrofuran until the washing liquid is clear, drying the filter cake, adding the filter cake and ethylenediamine into the reaction kettle, stirring at the rotation speed of 60-80r/min and the temperature of 100-80 ℃ for 30-40h to obtain a reactant, washing the reactant with ethanol until the washing liquid is clear, and drying the reactant to prepare the amino carbon nano tube;

step B3: mixing maleic anhydride and N, N-dimethylacetamide until the maleic anhydride is completely dissolved to obtain a maleic anhydride solution, adding the maleic anhydride solution into a reaction kettle, dropwise adding a second mixed acid at the rotation speed of 60-80r/min and the temperature of 50-55 ℃, wherein the dropwise adding time is 1-1.2h, continuously stirring for 15-20min after the dropwise adding is finished to obtain an intermediate 1, adding the intermediate 1 and a hydrochloric acid solution into the reaction kettle, stirring for 15-20min at the rotation speed of 60-80r/min and the temperature of 95-98 ℃, adding sodium hydroxide until the pH value of a reaction solution is 9-10, and filtering to remove filtrate to obtain an intermediate 2;

the reaction process is as follows:

step B4: adding chlorobenzene and the intermediate 2 prepared in the step B3 into a reaction kettle, stirring until the intermediate 2 is completely dissolved under the conditions that the rotation speed is 100-150r/min and the temperature is 35-45 ℃, introducing phosgene, heating to the temperature of 130-135 ℃ for reaction for 1-1.5h, and introducing nitrogen to remove the phosgene to prepare an intermediate 3;

the reaction process is as follows:

step B5: adding dibutyltin dichloride and toluene into a reaction kettle, stirring at the rotation speed of 100-200r/min and at the temperature of 40-50 ℃ until dibutyltin dichloride is completely dissolved, dropwise adding a sodium hydroxide solution, reacting for 2-3h to obtain an intermediate 4, adding the intermediate 4, tetrahydrofuran and the intermediate 3 prepared in the step B4 into the reaction kettle, reacting for 2-2.5h at the temperature of 50-60 ℃, and distilling at the temperature of 70-80 ℃ to remove tetrahydrofuran to obtain an intermediate 5;

the reaction process is as follows:

step B6: and B5, adding the intermediate 5 and tetrahydrofuran into a reaction kettle, stirring until the intermediate 5 is completely dissolved, adding N, N-diisopropylethylamine and the amino carbon nanotube prepared in the step B2, stirring for 20-30min under the conditions that the rotation speed is 150-200r/min and the temperature is 20-30 ℃, carrying out ultrasonic treatment for 5-10min under the condition that the frequency is 20-50kHz, filtering to remove filtrate, and drying a filter cake to obtain the heat-stable filler.

Further, the first mixed acid described in step B1 is a mixture of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:3, the mass fraction of the concentrated nitric acid is 68-70%, the mass fraction of the concentrated sulfuric acid is 70-75%, the dosage ratio of the thionyl chloride, N-dimethylformamide and the acidified carbon nanotube described in step B2 is 60mL:3mL:1-3g, the dosage ratio of the filter cake and ethylenediamine is 1-3g:120mL, the dosage ratio of the maleic anhydride and the second mixed acid described in step B3 is 1g:2-3mL, the second mixed acid is a mixture of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 9:10, the mass fraction of the concentrated nitric acid is 70-75%, the mass fraction of the concentrated sulfuric acid is 75-80%, the dosage ratio of the intermediate 1 and the hydrochloric acid solution is 1-1.5g:4mL, the mass fraction of the hydrochloric acid solution is 38-40%, the dosage ratio of the intermediate 2 and phosgene described in step B4 is 1:3, the mass ratio of the dibutyltin dichloride and the sodium hydroxide solution in the step B5 is 1:2, the mass fraction of the sodium hydroxide solution is 30-35%, the mass ratio of the intermediate 4 to the intermediate 3 is 1:1, the mass ratio of the intermediate 5 to the amino carbon nanotube in the step B6 is 5-6:3, and the amount of N, N-diisopropylethylamine is 5-8% of the total weight of the intermediate 5 and the amino carbon nanotube.

A preparation process of a reinforced nylon plate based on silicon-aluminum-based hollow microspheres comprises the following steps:

step S1: adding the silicon-aluminum-based hollow microspheres, the heat-stable filler, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring at the rotating speed of 300-500r/min until the silicon-aluminum-based hollow microspheres and the heat-stable filler are uniformly dispersed to prepare a dispersion liquid;

step S2: heating caprolactam at 75-80 ℃ until the caprolactam is completely melted, adding the dispersion liquid and the antistatic agent prepared in the step S1, stirring for 15-20min at the rotation speed of 100-150r/min, carrying out ultrasonic treatment for 5-10min at the frequency of 5-8MHz, heating to the temperature of 130-150 ℃, drying, pressing, and cooling to room temperature to obtain the nylon plate.

The invention has the beneficial effects that: the invention prepares a silicon-aluminum based hollow glass bead in the process of preparing a silicon-aluminum based hollow bead reinforced nylon plate, firstly aluminum chloride is dissolved in deionized water under the condition of ultrasonic treatment, then tetraethoxysilane is used as a raw material to prepare a silica sol, the silica sol is copolymerized with an aluminum chloride solution to obtain a silicon-aluminum based mixed solution, the silicon-aluminum based mixed solution and glass powder are mixed, so that silicon ions and aluminum ions are grafted on the glass bead, the friction resistance and impact resistance of the nylon plate are greatly enhanced, the service life of the nylon plate is further prolonged, a heat stable filler is prepared, the heat stable filler takes a carbon nano tube as a base material and is subjected to acidification treatment relative to the carbon nano tube, the acidified carbon nano tube is aminated, so that the surface of the carbon nano tube contains amino groups, an intermediate 5 is prepared, and the intermediate 5 is one of organic heat stabilizers, when the nylon plate is heated, the thermostable filler can capture macromolecular free radicals in the nylon plate, and then reacts with the macromolecular free radicals, so that the free radicals are terminated, and further the free radicals are prevented from continuing to react, thereby the heat-resisting effect is achieved, the amino carbon nanotube and the intermediate 5 are used for reacting, so that the amino and isocyanate groups react to ensure that molecules of the intermediate 5 are fixed on the carbon nanotube, and further the long-time use process of the nylon plate is ensured, the thermostable molecules can not be separated from the body, so that the service life of the nylon plate is prolonged, the nylon plate is not easy to separate out, and the environmental pollution is effectively avoided.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.